EP0485246B1 - Fabrication de fluoroéthylènes et de chlorofluoroéthylènes - Google Patents

Fabrication de fluoroéthylènes et de chlorofluoroéthylènes Download PDF

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Publication number
EP0485246B1
EP0485246B1 EP91402667A EP91402667A EP0485246B1 EP 0485246 B1 EP0485246 B1 EP 0485246B1 EP 91402667 A EP91402667 A EP 91402667A EP 91402667 A EP91402667 A EP 91402667A EP 0485246 B1 EP0485246 B1 EP 0485246B1
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EP
European Patent Office
Prior art keywords
catalyst
copper
process according
hydrogenolysis
hydrogen
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Expired - Lifetime
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EP91402667A
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German (de)
English (en)
French (fr)
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EP0485246A1 (fr
Inventor
Bernard Berthe
Jean-Marie Cognion
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Elf Atochem SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation

Definitions

  • the present invention relates to the preparation of fluoroethylenes and chlorofluoroethylenes by catalytic hydrogenolysis of chlorofluoroethanes or chlorofluoroethylenes.
  • patent EP 53657 describes a process for dehydrochlorination of F113 into chlorotrifluoroethylene (F1113) and trifluoroethylene (F1123) using a catalyst comprising a platinum group metal deposited on a support of the alkali magnesium fluoride type.
  • the results show a rapid deactivation of this catalyst with a significant formation of 1,1,2-trifluoroethane (F143) and 1-chloro-1,2,2-trifluoroethane (F133) as by-products, and this even for low conversion rates of F113.
  • patent EP 355 907 there is described a catalyst comprising a porous oxygenated support impregnated with a group VIII metal and a salt of an alkali or alkaline earth metal.
  • the examples given show conversion rates of F113 of the order of 50% and selectivities for F1113 and F1123 which do not exceed 80%.
  • the subject of the invention is therefore a process for the manufacture of fluoroethylenes and / or chlorofluoroethylenes by hydrogenolysis catalytic of a chlorofluoroethane of general formula: in which at least one of the symbols X, X ', Y and Y' represents a fluorine atom and the others, identical or different, each represent a hydrogen or chlorine atom, or of a chlorofluoroethylene of general formula : in which at least one of the symbols X, X ′ and Y represents a fluorine atom and the others, identical or different, each represent a hydrogen or chlorine atom, characterized in that a mixed catalyst is used based on copper or silver and at least one metal from the platinum group, preferably palladium, these metals being deposited on an activated carbon.
  • the content of copper and / or silver can range from 1 to 20% by weight, preferably between 3 and 15%, and that of metal of the platinum group can range from 0.1 to 10% by weight.
  • the conversion rate of chlorofluoroethane (I) or chlorofluoroethylene (II) varies in the same direction as the metal content of the platinum group; however, to avoid the concomitant formation of fluoroethanes, it is preferred to use a catalyst containing from 0.1 to 5% of said metal.
  • the activated carbon support can be in various forms such as, for example, extruded, pelletized, ground or balls.
  • the preparation of the mixed catalyst according to the invention is very simple and can be carried out in different ways, either by co-impregnation of the support with copper or silver and at least one metal from the platinum group, or by successive impregnation of the different metals.
  • the impregnation of the support can be carried out, for example, by soaking or spraying using a solution of salts of the metals to be deposited. This operation can be carried out at a temperature ranging from approximately 20 to 80 ° C., but is preferably carried out at ambient temperature.
  • the solvent which is preferably water, but can also be a hydrocarbon, a light alcohol or a ketone, is then evaporated under vacuum, gradually raising the temperature.
  • the catalyst is reduced under a stream of hydrogen (10 to 80 l / h per 100 g of catalyst) at a temperature between 100 and 500 ° C.
  • chlorides are advantageously used.
  • other salts for example, nitrates, acetates, acetylacetonates
  • Another method of preparing a catalyst according to the invention consists in starting from a commercial catalyst based on the supported platinum group metal and in impregnating it with a solution of a copper or silver salt, l 'Evaporation of the solvent and the final reduction being carried out in the same way as in the case of co-impregnation.
  • the catalyst according to the invention can be used according to any hydrogenolysis technique such as, in particular, those operating in a fixed bed or in a fluidized bed.
  • the hydrogenolysis can be carried out at a temperature ranging from 100 to 400 ° C, preferably between 150 and 350 ° C. It is advantageous to operate at atmospheric pressure, but it would not depart from the scope of the present invention by working at sub- or superatmospheric pressure.
  • the molar ratio between hydrogen and chlorofluoroethane (I) or chlorofluoroethylene (II) is generally between 0.1 and 10, preferably between 0.5 and 5.
  • the contact time can vary between 1 and 45 seconds, but excellent results have been obtained with contact times between 2 and 10 seconds.
  • a CECA activated carbon having a porosity of 0.6 cm3 / g and a specific surface of 950 m2 / g, in the form of extrudates of 1.8 mm in diameter, are loaded into a rotary evaporator.
  • 70 ml of an aqueous solution containing 2.96 g of palladium chloride and 2.7 g of hydrated cupric chloride (CuCl2, 2H2O) are introduced, then the water is evaporated under reduced pressure (1 kPa) and dried to 100 ° C. Then treated at 450 ° C for 3 hours under a stream of hydrogen (10 l / h) and a catalyst is obtained, ready for use, containing 7% palladium and 4% copper.
  • the main by-product is F123a (CF2Cl-CFClH) which can be recycled to the reactor to form F1123.
  • Example 1B The procedure is as in Example 1B to hydrogenolyze F1113 with 1.26 ml of the catalyst of Example 2A.
  • Example 1B The procedure is as in Example 1B for the hydrogenolysis of F132b (CF2Cl-CH2Cl) with 1.26 ml of the catalyst of Example 1A.
  • Example 1A 25 ml (13.5 g) of the catalyst described in Example 1A are introduced into the same reactor as in Example 5 and the hydrogenolysis of F113 is carried out at atmospheric pressure.
  • Example 6 is repeated with 25 ml (13.5 g) of the catalyst described in Example 2A.
  • the following table brings together the operating conditions and the results obtained.
  • Total flow (mole / hour) F113 transformation rate (%)
  • Selectivity in F1113 (%) F1123 (%) 350 3 0.72 100 60.5 39.2 350 3.1 0.31 100 50.5 48.2 350 3 0.15 100 41 57 350 3 0.08 100 39.1 58.3
  • Example 8A The procedure is as in Example 8A, but replacing the aqueous solution of palladium chloride and cupric chloride with 100 ml of a pyridine solution containing 4.17 g of silver acetate and 0.506 g of palladium acetate .
  • Example 8A The procedure is as in Example 8A, but replacing the aqueous solution of palladium chloride and cupric chloride with 100 ml of an aqueous solution containing 0.5 g of hydrated ruthenium chloride (Ru content: 41.5% ) and 7.3 g of hydrated cupric chloride (CuCl2, 2H2O).
  • Example 8A The procedure is as in Example 8A, but replacing the aqueous solution of palladium chloride and cupric chloride with 100 ml of an aqueous solution containing 0.65 g of chloroplatinic acid hexahydrate (H2PtCl6, 6H2O) and 7.25 g of hydrated cupric chloride (CuCl2, 2H2O).
  • 26 g of a CECA activated carbon having a porosity of 0.22 cm3 / g and a specific surface of 1000 m2 / g, in the form of cassettes of 2 to 2.5 mm, are loaded into a rotary evaporator.
  • 100 ml of an aqueous solution containing 0.61 g of hydrated rhodium chloride RhCl3 (40.4% rhodium) and 7.29 g of cupric chloride hydrate (CuCl2, 2H2O) are introduced, then the water is evaporated under reduced pressure (1kPa) and dried at 100 ° C. Then treated at 450 ° C for 3 hours under a stream of hydrogen (10 l / h) and a catalyst is obtained, ready for use, containing 0.85% rhodium and 9.4% copper.
EP91402667A 1990-11-06 1991-10-07 Fabrication de fluoroéthylènes et de chlorofluoroéthylènes Expired - Lifetime EP0485246B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9013705 1990-11-06
FR9013705A FR2668769B1 (fr) 1990-11-06 1990-11-06 Fabrication de fluoroethylenes et de chlorofluoroethylenes.

Publications (2)

Publication Number Publication Date
EP0485246A1 EP0485246A1 (fr) 1992-05-13
EP0485246B1 true EP0485246B1 (fr) 1994-12-14

Family

ID=9401870

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91402667A Expired - Lifetime EP0485246B1 (fr) 1990-11-06 1991-10-07 Fabrication de fluoroéthylènes et de chlorofluoroéthylènes

Country Status (12)

Country Link
US (1) US5315045A (pt)
EP (1) EP0485246B1 (pt)
JP (1) JPH0813762B2 (pt)
AT (1) ATE115533T1 (pt)
CA (1) CA2054828C (pt)
DE (1) DE69105923T2 (pt)
DK (1) DK0485246T3 (pt)
ES (1) ES2066393T3 (pt)
FR (1) FR2668769B1 (pt)
GR (1) GR3015211T3 (pt)
IE (1) IE69121B1 (pt)
PT (1) PT99430B (pt)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1005238A3 (fr) * 1991-01-25 1993-06-08 Solvay Procede pour la preparation de chlorotrifluoroethylene et de trifluoroethylene au depart de 1,1,2-trichloro-1,1,2-trifluoroethane et composition catalytique utilisee dans ce procede.
US5453557A (en) * 1992-10-01 1995-09-26 The Dow Chemical Company Processes for converting chlorinated byproducts and waste products to useful materials
US5892135A (en) * 1996-08-23 1999-04-06 E. I. Du Pont De Nemours And Company Process for the production of trifluoroethylene
CN102086144A (zh) * 2004-08-26 2011-06-08 纳幕尔杜邦公司 化学生产方法和系统
US7795482B2 (en) * 2007-07-03 2010-09-14 E. I. Du Pont De Nemours And Company Method of hydrodechlorination to produce dihydrofluorinated olefins
FR2937033B1 (fr) * 2008-10-13 2010-10-22 Arkema France Procede de preparation de fluorure de vinylidene.
US20100324345A1 (en) * 2009-06-22 2010-12-23 Honeywell International Inc. SYSTEMS AND PROCESSES FOR CFO-1113 FORMATION FROM HCFC-123a
US20130131402A1 (en) * 2010-07-01 2013-05-23 Solvay Specialty Polymers Italy S.P.A. Process for the synthesis of trifluoroethylene
FR2987358B1 (fr) * 2012-02-28 2016-10-21 Arkema France Procede de synthese du trifluoroethylene a partir du chlorotrifluoroethylene
CN109415282A (zh) * 2016-07-11 2019-03-01 大金工业株式会社 1－氯－1,2－二氟乙烯的制造方法
JP7348535B2 (ja) * 2021-07-15 2023-09-21 ダイキン工業株式会社 アルケンの製造方法
WO2023112433A1 (ja) * 2021-12-14 2023-06-22 Ａｇｃ株式会社 １，２－ジクロロー１，２－ジフルオロエチレンの水素置換体の製造方法
WO2023149559A1 (ja) * 2022-02-04 2023-08-10 エヌ・イーケムキャット株式会社 水素化反応用触媒およびその製造方法、ならびに水素化有機化合物の製造方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA655397A (en) * 1963-01-08 H. Pearson John Manufacture of chf=cf2
US2704775A (en) * 1951-02-02 1955-03-22 Union Carbide & Carbon Corp Preparation of halogenated olefines
US2697124A (en) * 1952-02-25 1954-12-14 Kellogg M W Co Dehalogenation of fluorohalocarbons
US2802887A (en) * 1955-08-08 1957-08-13 Allied Chem & Dye Corp Hydrogenation of chlorotrifluoroethylene
JPS462324B1 (pt) * 1966-12-16 1971-01-21
DE3170139D1 (en) * 1980-12-09 1985-05-30 Allied Corp Preparation of chlorotrifluoroethylene and trifluoroethylene
IT1186307B (it) * 1985-06-10 1987-11-26 Montefluos Spa Procedimento per la preparazione di 1,2-difluoroetilene e 1-cloro-1,2-difluoro-etilene
IT1196518B (it) * 1986-07-18 1988-11-16 Ausimont Spa Preparazione di fluoroetileni e clorofluoroetileni da clorofluoroetani
EP0459463B1 (en) * 1990-05-31 1994-08-17 Daikin Industries, Limited Process for preparing 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene

Also Published As

Publication number Publication date
DE69105923D1 (de) 1995-01-26
IE913863A1 (en) 1992-05-22
IE69121B1 (en) 1996-08-07
JPH04288028A (ja) 1992-10-13
ATE115533T1 (de) 1994-12-15
FR2668769A1 (fr) 1992-05-07
CA2054828A1 (fr) 1992-05-07
US5315045A (en) 1994-05-24
CA2054828C (fr) 1996-10-22
EP0485246A1 (fr) 1992-05-13
DK0485246T3 (da) 1995-05-15
FR2668769B1 (fr) 1992-12-31
PT99430A (pt) 1992-09-30
JPH0813762B2 (ja) 1996-02-14
DE69105923T2 (de) 1995-07-13
GR3015211T3 (en) 1995-05-31
ES2066393T3 (es) 1995-03-01
PT99430B (pt) 1999-04-30

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